Yellow-colored magenta-forming couplers



Patented May 9, 1961 United States Patent There is formed in this way adye image consisting of the new dye and the residual colored coupler.The

2,983,608 theory of color correction requires that the absorption of pthe residual colored coupler and the undesired absorp- E%%%%EE 5 tion ofthe image dye should be constant. This requirement is not alwaysfulfilled by colored couplers in use Leo E. Beavers, Rochester, N.Y.,assignor to Eastman so errors are introduced in the process of colorKodak Company, Rochester, N.Y., a corporation of correction New JerseyMagenta dyes produced upon color development have an undesiredabsorption of light in the blue region of No Drawmg' Filed 1958 set.765,315 the spectrum. Therefore, it is desirable to have yellow- 13Claims. (Cl. 96-100) colored magenta-forming coupler compounds that canbe used to correct for this unwanted blue absorption.

Yellow-colored magenta-forming coupler compounds This invention relatesto color photography and par- 15 made from colorless magenta-formingcoupler compounds ticularly to colored color couplers for use inphotographic that are incorporated in certain color negative materialsprocesses. are insufliciently reactive to give the desired color correc-Color-forming compounds which react with the tive masking effects. Forexample, in a typical case, an development product of aromatic aminodeveloping agents unwanted blue absorption of 0.28 density units isproduced to form colored images upon photographic development by themagenta dye formed from the reaction of the are well known, Generallythese color-forming comoxidized primary aromatic amino developing agentwith pounds of couplers are colorless or substantially colortheuncolored magenta-forming Coupler A:

1 (2,4,6'-trichlorophenyl) -3 [3" (2",4"'-di-amylpheuoxyacetamido)benzamido] -5-pyrazo1one less. This lack of color is usually desirablewhen the In an ideal situation enough blue absorbing colored coupler isto be incorporated in the emulsion layer and coupler is mixed with thecolorless coupler to compensate the unused coupler remains afterformation of the colored for this unwanted absorption as described inVittum and image, Arnold, US. Patent 2,428,054 and Hansen, US. PatentCouplers which are in themselves more or less strongly 2,449,966.However, the yellow-colored magenta-formcolored and which contain achromophore group which ing Coupler B:

o 01 H N=CNHO 0 01 l Nnii on 0 o H 1 on H Q u g 1R- EH111(2',4',6'-triehlorophenyl -3 [3"-(2"',4" '-di-amylphenoxyacetamido)benzamido] -4-( -n1ethoxyphenylazo) -5-pyrazolone is split off ordestroyed during and by means of the coupling reaction with the resultthat the original color of the coupler is destroyed and a new dye isformed upon coupling are disclosed in Glass, 2,455,170, Hansen,2,449,966, and Heimbaeh et al. 2,688,539.

Upon development of an emulsion layer containing one of these coloredcouplers, the coupler color is usually destroyed and a new color isformed by the coupling reaction of those points where developmentoccurs.

derived from uncolored coupler is insuificiently reactive V and aresidual amount raises the blue absorption in the exposed area from 0.28to 0.43 density units. Consequently, the colored Coupler B must be usedin a con centration that is sufficient to give a density of 0.43 inunexposed regions. This situation prevails when the ratio of Coupler Bto coupler incorporating solvent is 1:2. At the desired ratio of 12% thecolored Coupler B is completely unreactive and gives no colorcorrection.

Furthermore, it is desired to have yellow-colored magenta-formingcouplers with higher extinction coefficients than the available coloredcouplers.

It is, therefore, an object of the present invention to provide a classof yellow-colored magenta-forming couplers for use with uncoloredmagenta-forming couplers to correct for the deficiencies in the magentadye produced upon color development. A further object is to provide aclass of yellow-colored magenta-forming couplers which are sufiicientlyreactive to give complete compensation for the unwanted blue absorptionof the magenta dye produced upon colored development at the desiredcoupler to coupler incorporating solvent ratio of 11 /4 A still furtherobject is to provide a yellow-colored magenta-forming coupler with ahigher extinction co efficient than the available coloredmagenta-forming couplers. A still further object is to provide a classof yellow-colored magenta-forming couplers which because of theirsuperior characteristics can be used for color correction in colorphotographic products in thinner emulsion coatings to give aphotographic product having a lower minimum density than would bepossible with known colored magenta-forming couplers, Other objects willappear from the following description and claims.

These and other objects are accomplished by means of this invention asdescribed hereinafter. We have discovered that couplers of the3-anilino-4-arylazo-5- pyrazolone type are valuable yellow-coloredmagentaforming couplers. Our couplers are not only yellowcolored but arecharacterized by being completely reactive with the oxidized primaryaromatic amino developing agents, even when used at a coupler to couplerincorporating solvent ratio of I:%. For example, our Coupler I iscompletely reactive at a coupler to coupler incorporating solvent ratioof 12% and gives complete compensation for the unwanted blue absorptionof the magenta dye when incorporated in sufficient amount to have thedensity of 0.28 units to blue light. These characteristics are entirelyunexpected because of the vary small chemical differences between ourCoupler I and Coupler B which is completely unreactive at coupler tocoupler incorporating solvent ratios of 1:% and therefore gives no colorcorrection.

Our couplers are not only valuable because of their reactivity butbecause they have higher extinction co-efiicients than do thecorresponding 3-benzamido-5-pyrazolone type of coupler. For example, ourCoupler I has an extinction co-efiicient of 2.8 in butyl acetate ascompared to an extinction coefiicient of 1.5 X 10 in butyl acetate givenby Coupler B.

The characteristics shown by our couplers give their user valuableadvantages over one using the yellow-colored magenta-forming couplercompounds known before. For example, smaller amounts of our coupler canbe used than similar couplers outside the invention. In addition tothis, the products in which our couplers are used are improved becausethey have a lower minimum emulsion layers. Thinner emulsion layers areoften desirably employed for giving images with improved definition andresolution.

The preferred embodiments of this invention have the wherein R is anaryl group such as a phenyl radical or a phenyl radical substituted atthe 2,4, and 6 carbons with halogen atoms, such as a2,4,6-trichlorophenyl, a 2,4,6- tribromophenyl, a 2,4,6-triiodophenyl ora 2,4,6-trifiuorophenyl group; R is a hydrogen atom or an alkyl grouphaving from 1-8 carbon atoms but preferably from 1-4 carbon atoms; X, Yand Z are hydrogen atoms and alkyl radicals usually having from l20carbon atoms but preferably 1-15 with at least one of the substituentsX, Y and Z being an alkyl radical; R" is a hydrogen atom, an alkyl or analkoxy radical usually having from 1-10 carbon atoms but preferably from1-6 carbon atoms.

In addition to the preferred embodiments defined above, this inventionalso includes compounds of the above formula wherein R is a phenyl groupsubstituted at the 2, 4, and 6 carbons with alkyl or alkoxy radicalsusually having from l-6 carbon atoms, aryl groups, aryloxy groups, cyanogroups, carbalkoxy groups, or nitro groups; and where R is an acylamidogroup, a carbalkoxy group, a dialkylamino group, an arylether group orother electron-donating substituent.

The yellow color of our couplers is destroyed upon reaction with anoxidized primary aromatic amino developing agent and a magenta-coloreddye is formed. Although the exact mechanism of this reaction is notcompletely understood, it appears as though the reaction may proceed asfollows:

N=G-R'" Step 1.1-(2,4,6 trichlorophenyl) -3-a.mino-5-pyrazo- Q l lone isprepared by the reaction A) I 5 o-GaHs 0 NaOCzH; Cl- NHNHz-I- HCHMJ 1 NHOCgHs C1 T /l\=C-NH HzC-N-CH; 01- N\ 1 o: H N wherein R represents thegroups described by the gen- 8 eral formula and R represents the groupsdescribed as Ompmmd A being substituted on the carbon atom in the 3position of the S-pyrazolone of the general formula. The compounds ofthis invention can be used in ad- 01 mixture with the uneolored couplerswhich appear to g /N=C-NH: react as fOllOWSi 2O CompoundA-i-OEhO -)Cl N\+oH3o H 0- H2 Na Q l Compound B Procedure N=CR Q 39 In a 5-1. flaskequipped with a reflux condenser is placed 317 g. (1.5 moles) of2,4,6-trichlorophenylhyg H drazine, 249 g. (1.65 moles) of ethylfi-ethoxy-;8-imino- N propionate, 950 cc. of absolute ethanol, and 5 cc.of

glacial acetic acid. The reaction is refluxed 2.5 hours.

Meanwhile, 69 g. (3.0 moles) of sodium is reacted with 1100 cc. ofabsolute ethanol and added cautiously through the condenser after theoriginal reflux. The

alkaline solution is refluxed 1 hour, diluted with l 1. of

HBCN'OH3 warm water, acidified with 190 cc. of glacial acetic acid, 40and cooled to 5. The solid is filtered, Washed with cold water anddried. The yield is 317 g. of pink crystals,

wherein R' represent the groups defined above. melting at 222-224".Concentration of the liquors to A Typical compounds embodying theinvention and which volume and dilution with 500 cc. of Water gives 51g. of can be used according to the invention include the folpink solidmelting at 2l8220. lowing which illustrate the invention but to whichthe Step 2.l (2',4,6'-trichlorophenyl)-3(4"-nitropheninvention is notlimited: oxy)acetarnido-5-pyrazolone is prepared by the reaction COUPLERI O 02H; 01 r g 1 (22426 trlchlorophenyl) 3 {4" [a(2"',4"' d1tertiaryamylphenoxy) butyramidoJanfllno} 4 (4""methoxyphenyl)azo-5-pyrazo1one [Melting point, 218.5-221 0.] (I? A t 1 cetoni ri eCompoundB+C10GHz-O N0 Percent Composition Calculated Found h t 01 ll 2.&3 6.3 N=o-NHo-oH,-0 N 10. 4 11.1 or 13.1 11.3

C-CH:

A typical process for preparing Coupler I is as follows: q d 0 .7 IProcedure aminoanilino)--pyrazolone is prepared by the reaction-Compound D+3Hr-- A 500-m1. 3-necked flask is equipped with a stirrer, C1dropping funnel and water-cooled condenser. The flask 5 i is chargedwith 55.6 g. (.2 mole) of 1-(2,4,6-trichloro- +2H 0phenyl)-3-amino-5-pyrazolone, and 200 ml. of dry ace- ()1 1 2 tonitrileand heated at reflux over a steam bath with O mechanical stirring. Asolution of 47 g. (.2 mole) of or: CmpmmdE (p-nitrophenoxy)acetylchloride, in 100 ml. of dry aceprocedure tonitrile is added from thedropping funnel in mm. Solution is complete at this point, but soon aprecipitate A solution of 1 0 g (0.025 mole) of 1-(2',4',6'-tr1- startsto form. After 4 hours the precepitate is filtered P YD -PY 200 from thehot mixture, and washed on the funnel first with 1 cc. of alcholo 1shydrogenated for 3 hours at 40 p.s.1. and 100 ml. of fresh acetonitrileand then with about 2 liters 40 The catalyst 13 filtered 0E and fiitrate.concentrat' f Water The crude 6, trichlomphenyl) 3 [w ed to 50 cc.under vacuum. The solid is redissolved on O heating then separated oncoohng givlng 5.1 g. of 1-(2', (4 -n1trophenoxy)acetam1do]-5-pyrazo1one1s crystall zed 4l,6l trichlorophenyl) 3 (4 aminoanflin0) 5 pyrazolonefrom 90 percent acetic acid (50 ml./g.) to give a purified 20 with avMpof Product meltlllg at Step 5. From this compound 1-(2',4',6'-t1ichloro-Step 3. 1-(2',4',6'-trichlorophenyl)-3-(4"-nitroaniphenyl) 3{4"[a-(2",4"'-di-tert. amylphenoxy)butyrlino)-5-pyrazolone is preparedby the reactionamido]anilino}-5-pyrazolone is made by the reaction 0CzHs Compound E+CI(I(IJH-O CsHn(t)- C H t a 11() Cl 0 02H /N=C-NHNHC--CH-O 0.11110) C l cm (a Compound]? Compound O+Na0 H---- Procedure Amixture of 5.7 g. 0.154 mole) of 1-(2',4',6'-tri; 01 chlorophenyl)-3 (4"aminoanilino) 5 pyrazolone and 5.23 g. (0.154 mole) ofa-(2,4-di-tertiaryamylphenoxy) O-CH2 butyryl chloride in 250 cc. ofacetonitrile is refluxed for 01 ll 0 7 /2 hours then allowed to-standfor 16 hours followed by Com 01m (113 2 hours additional refluxing. Thereaction mixture is p evaporated to dryness in vacuo. The residue isdissolved in 25 cc. of acetone and 200 cc. of hexane (from petroleum) isadded. The mixture is digested in a steam Procedure bath untilcrystallization occurs. On cooling the crude product separates.Alternating recrystallization from A 12-1it fl k equipped ith a me hanial tirrer is acetone-hexane and from acetonitn'le gives 6.0 g. of tinycharged with 840 cc. of water, 3.2 l. of 3-A alcohol and Whlte crystalsmeltlngfit 352 g. (8.8 moles) of freshly opened sodium hydroxide Step 6-COUPler I is made by the (c.p.). The solution formed on stirring iscooled to room temperature and 2 Kg (4.38 moles) of 1-(2,4,6'-triou dF+0 a0-Ni01 Gou 1erI chlorophenyl)-3-[m-(4"-nitrophenoxy)acetamido] 5pyrafomnefs i After bemg smied Overmght the To asolution of 1.34 g.0.002 mole) of 1-(2,4',6-trireaction nuxture 1s filtered and the SOildwashed on the chlorophenyl) 3 (2!n di tertiar am funnel with 3-A alcoholunit most of the red color is y y w h d out The combined filtrate andWashin s are phenoxy)-butyramido]an111no}-5-pyrazolone in 27 cc. of as dI 1 id th Odu t I pyridine is added during /2 hour at 05 to thetheoretii s 128 f aclal ace 2 e r S cal amount of diazotized4-methoxyaniline. The mixture ecte on a app mme was 6 W1 ace 10 an isstirred for 3 hours then drowned in ice and water to dried. This crudeproduct is recrystallized by dissolving in 3 l. of warmN,N-dimethylformamide and adding 30 l. of 3-A alcohol at roomtemperature, yielding 1240 g. with a M.P. of 299-304.

give 1.6 g. of crude product. This solid is crystallized twice fromacetonitrile giving 0.6 g. of l-(2',4',6'-trichlorophenyl) 3 {4"[a(2"',4' di tertiaryamylphenoxy) butyramido] anilino}-4-( 4methoxyphenyl) azo Step 4. 1 (2',4',6' trichlorophenyl) 3 (4"S-pyrazolone, with a M.P. of 218.5- -221 C.

NHC-CH-O Cl N lHn (t) IL it 1 (2',4',=6' trlchlorophenyl) 3 {4 [a(2",4"'di tertiaryamylphenoxy)butyramido]aniline} 4 (4""dodecoxyphenyDazo-Ei-pyrazolone [Melting point, 98.-102. (3.]

[Melting point, 166.-168.) 0.]

Percent Composition Calculated Found Pereent Composition CalculatedFound (J 66.3 66.7 0.. 71.7 71.4 7. 3 7. 3 H 7.1 7. 0 N. 8. 8 9. 3 N12.0 12. 2 O] 11.1 1L0 0... 9.1 9.6

Coupler VI is prepared by the procedure described Couplers II, III, IVand V are prepared according to the procedure described for Coupler Iexcepting that Compound F is reacted in Step 6 with the appropriate forthe Coupler I synthesis.

COUPLER vn 1 (25456 trichlorophenyl) s 4" mz'" 4'" 11- terondaryamylphenyl)azo diazonium chloride compound as shown in the following[Melting point, 144.148. 0.]

for Coupler I except that in Step 1 phenyl hydrazine is used in place ofthe 2,4,6-trichlorophenylhydrazine used N=I -NH NHC- 11-0 CaHMt) table:

Coupler Diazonium Chloride Used in Step 6 of Synthesis PercentComposition Calculated Found 4-ethoxy benzene diazonium chloride. C. 65.5 65. 3 2-ethoxy benzene diazonium chloride. FT 6. 6 6. 5 4-butoxybenzene diazonium chloride. N. 10.0 10. 3 4-dodeeoxy benzene diazoniumchloride. C 12. 6 12.8

COUPLER VI 0 CaHn CHa Coupler VII is prepared by the procedure describedfor Coupler I excepting that Compound F is reacted in Step 6 with4-secondary amyl benzene diazonium chloride.

Our yellow-colored magenta-forming coupler compounds can be used in anyphotographic emulsion where magenta-forming couplers are used or can beused. Usually these couplers are used in admixture with uncoloredmagenta-forming couplers. Colored and uncolored couplers are selectedwhich form either the same magenta dye upon color development or amagenta dye of the same hue. These photographic emulsions producingcolor corrected magenta images can be used alone, however, they areusually used in combination with photographic elements forming a yellowimage, and a cyan or corrected cyan image to produce a colored picture.

The following examples illustrate a typical way in which our couplerscan be incorporated and used in color photographic material:

EXAMPLE I 0.25 gram of our yellow-colored magenta-forming Coupler I and0.25 gram of the uncolored magentaforming coupler1(2,4',6'-trichlorophenyl)-3[3"-(2", 4"'-diamylphenoxyacetamido)benzamidoJ-S-pyrazolone were dissolved in 1 gram of tri-o-cresylphosphate with stirring at 110 C. This solution was intimately mixedwith and dispersed in a solution containing 22 ml. of 10% gelatin and 2ml. of .5% Alkanol B. 2 ml. of 7.5% saponin and 15 ml. of water wereadded to this dispersion. 25 ml. of this dispersion was added to ml. ofa medium speed silver bromoiodide emulsion and this was coated on acellulose acetate support and dried.

The coating was given an image exposure and developed in an alkalinedeveloper solution containing 2- amino-S-(N-ethyl-N-B-methanesulfonamidoethyl)toluene sulfate, to form a negative silver and magentadye image and a yellow-positive dye image. The silver image and theresidual silver halide were removed by treating film in a ferri cyanidebleach followed by hypo fix. This left a negative image in magenta dyehaving maximum absorption at a wavelength of 534 mg, and a positiveimage in residual yellow-colored coupler having a maximum absorption at430 mu.

EXAMPLE II Similar results were obtained by using a dispersion made bydissolving 0.25 gram of our yellow-colored magenta-forming Coupler I and0.25 gram of the uncolored magenta-forming coupler 1(2',4',6'-trichlorophenyl) 3 [3-(2",4"'-diamylphenoxyacetamido)- benzamido]-5-pyrazolone in0.125 gram of tri-o-cresyl phosphate and 4 ml. of ethyl acetate. Thissolution was added to the same amount of gelatin solution and theemulsion as in Example I, and coated in the same manner. The ethylacetate evaporated from the coating on drying. The same exposure andprocessing conditions yielded a negative magenta dye image havingmaximum absorption of at least 540 m and a positive yellow image withmaximum at 430 mu.

The couplers of our invention are used in photographic emulsions of thedeveloping out type.

The emulsions can be chemically sensitized by any of the acceptedprocedures. The emulsions can be digested with naturally active gelatin,or sulfur compounds can be added such as those described in SheppardU.S. Patent 1,574,944; Sheppard and Punnett U.S. Patent 1,623,499; andSheppard and Brigham U.S. Patent 2,410,689.

The emulsions can also be treated with salts of the noble metals such asruthenium, rhodium, palladium, iridium, and platinum. Representativecompounds are ammonium chloropalladate, potassium chloroplatinate, andSodium chloropalladite, Which are used for sensitiz- 14 ing in amountsbelow that which produces any substantial fog inhibition, as describedin Smith and Trivelli U.S. Patent 2,448,060, and as antiioggants inhigher amounts, as described in Trivelli and Smith U.S. Patents2,566,245 and 2,566,263.

The emulsions can also be chemically sensitized with gold salts asdescribed in Waller, Collins, and Dodd U.S. Patent 2,399,083 orstabilized with gold salts as described in Damschroder U.S. Patent2,597,856 and Yutzy and Leermakers U.S. Patent 2,597,915. Suitablecompounds are potassium chloroaurite, potassium aurithiocyanate,potassium chloroaurate, auric trichloride and 2-aurosulfobenzothiazolemethochloride.

The emulsions can also be chemically sensitized with reducing agentssuch as stannous salts (Carroll U.S. Patent 2,487,850), polyamines, suchas diethylene triamine (Lowe and Jones U.S. Patent 2,518,698),polyamines, such as spermine (Lowe and Allen U.S. Patent 2,521,925), orbis(5-aminoethyl) sulfide and its watersoluble salts (Lowe and JonesU.S. Patent 2,521,926).

The emulsions can also be optically sensitized with cyanine andmerocyanine dyes, such as those described in Brooker U.S. Patents1,846,301; 1,846,302; and 1,942- 854; White U.S. Patent 1,990,507;Brooker and White U.S. Patents 2,112,140; 2,165,338; 2,493,747; and2,739,- 964; Brooker and Keyes U.S. Patent 2,493,748; Sprague U.S.Patents 2,503,776 and 2,519,001; Heseltine and Brooker U.S. Patent2,666,761; Hesseltiue U.S. Patent 2,734,900; VanLare U.S. Patent2,739,149; and Kodak Limited British 450,958.

The emulsions can also be stabilized with the mercury compounds ofAllen, Byers, and Murray U.S. Patent 2,728,663; Carroll and Murray U.S.Patent 2,728,664, and Leubner and Murray U.S. Patent 2,728,665; thetriazoles of Heimbach and Kelly U.S. Patent 2,444,608; the azaindenes ofHeimbach and Kelly U.S. Patents 2,444,605 and 2,444,606; Heimbach U.S.Patents 2,444,- 607 and 2,450,397; Heimbach and Clark U.S. Patent2,444,609; Allen and Reynolds U.S. Patents 2,713,541 and 2,743,181;Carroll and Beach U.S. Patent 2,716,062; Allen and Beilfuss U.S. Patent2,735,769; Reynolds and Sagal U.S. Patent 2,756,147; Allen and SaguraU.S. Patent 2,772,164, and those disclosed by Birr in the Z. wiss. Phot.47, 2(1952); the quaternary b-enzothiazolium compounds of Brooker andStand U.S. Patent 2,131,038; and the zinc and cadmium salts of JonesU.S. Patent 2,839,405.

The emulsions may also contain speed-increasing compounds of thequaternary ammonium type of Carroll U.S. Patent 2,271,623; Carroll andAllen U.S. Patent 2,288,226; and Carroll and Spence U.S. Patent2,334,864; and the polyethylene glycol type of Carroll and Beach U.S.Patent 2,708,162.

The emulsions may contain a suitable gelatin plasticizer such asglycerin; a dihydroxy alkane such as 1,5-pentane diol as described inU.S. application Serial No. 588,951 of Milton and Murray; an ester of anethylene bis-glycolic acid such as ethylene bis(methyl glycolate) asdescribed in U.S. application Serial No. 662,564 of Milton; bis-(ethoxydiethylene glycol) succinate as described in Gray U.S. Patent 2,940,854or a polymeric hydrosol as results from the emulsion polymerization of amixture of an amide of an acid of the acrylic acid series, an acrylicacid ester and a styrene-type compound as described in Long U.S. Patent2,852,386. The plasticizer may be added to the emulsion before or afterthe addition of a sensitizing dye, if used. Y

The emulsion may be hardened with any suitable hardener for gelatin suchas formaldehyde; a halogensubstituted aliphatic acid such as mucobromicacid as described in U.S. Patent 2,080,019 of White; a compound having aplurality of acid anhydride groups such as 7,8-diphenylbicyclo(2,2,2)-7-octene 2,3,5,6 tetracarboxylic dianhydride, ora dicarboxylic or a disulfonic acid chloride such as terephthaloylchloride or naphthalene-1,5-

disulfonyl chloride as described in U.S. Patents 2,725,- 294 and2,725,295 of Allen and Carroll; a cyclic 1,2- diketone such ascyclopentane-1,2-dione as described in U.S. Patent 2,725,305 of Allenand Byers; a bisestcr of methane-sulfonic acid such as1,2-di-(methanesulfonoxy)- ethane as described in U.S. Patent 2,726,162of Allen and Laakso; 1,3-dihydroxymethylbenzimidazole-2-one as describedin U.S. Patent 2,732,316 of July, Knott and Pollak; a dialdehyde or asodium bisulfite derivative thereof, the aldehyde groups of which areseparated by 2-3 carbon atoms such as B-methyl glutaraldehyde bissodiumbisulfite as described in U.S. application Serial No. 556,031 of Allenand Burness; a bis-aziridine carboxamide such as trirnethylenebis(1-aziridine carboxamide) as described in U.S. application Serial No.599,- 891 of Allen and Webster; or 2,3-dihydroxy dioxane as described inJefireys U.S. Patent 2,870,013.

The emulsions may have been supplied with a coating aid such as saponin;a lauryl or oleyl monoether of polyethylene glycol as described in U.S.Patent 2,831,766 of Knox and Davis; a salt of a sulfated and alkylatedpolyethylene glycol ether as described in U.S. Patent 2,719,- 087 ofKnox and Davis; an acylated alkyl taurine such as the sodium salt ofN-oleoyl-N-methyl taurine as described in U.S. Patent 2,739,891 of Knox,Twardokus, and Davis; the reaction product of a dianhydride oftetracarboxybutane with an alcohol or an aliphatic amine containing from8 to 18 carbon atoms which is treated with a base, for example, thesodium salt of the monoester of tetracarboxybutane as described in Knox,Stenberg, and Wilson U.S. Patent 2,843,487; a water-solublemaleopimarate or a mixture of a Water-soluble maleopimarate and asubstituted glutamate salt as described in U.S. Patent 2,823,123 of Knoxand Fowler; an alkali metal salt of a substituted amino acid such asdisodium N- (carbo-p-tert.octylphenoxypentaethoxy) glutamate asdescribed in U.S. application Serial No. 600,679 of Knox and Wilson; ora sulfosuccinamate such as tetrasodiumN-(1,2-dicarboxyethyl)-N-octadecyl sulfosuccinamate or N-lauryl disodiumsulfosuccinamate as described in U.S. application Serial No. 691,125 ofKnox and Stenbcrg.

The couplers which we have described may be used in various kinds ofphotographic emulsions. Various silver salts may be used as thesensitive salt such as silver bromide, silver iodide, silver chloride,or mixed silver halides such as silver chlorobromide or silverbromoiodide. The couplers can be used in emulsions of the mixed-packettype, such as described in Godowsky U.S. Patent 2,696,794 or emulsionsof the mixed-grain type, such as described in Carroll and Hanson U.S.Patent 2,592,243. These agents can also be used in emulsions which formlatent images predominantly on the surface of the silver halide crystalor in emulsions which form latent images predominantly inside the silverhalide crystal, such as those described in Davey and Knott U.S. Patent2,592,250.

In the preparation of the silver halide dispersions employed forpreparing silver halide emulsions there may be employed as thedispersing agent for the silver halide in its preparation, gelatin orsome other colloidal material such as colloidal albumin, a cellulosederivative, or a synthetic resin, for instance, a polyvinyl compound.Some colloids which may be used are polyvinyl alcohol or a hydrolyzedpolyvinyl acetate as described in U.S. Patent 2,286,215 of Lowe; a farhydrolyzed cellulose ester such as cellulose acetate hydrolyzed to anacetyl content of 19-26% as described in U.S. Patent 2,327,808 of Loweand Clark, a water-soluble ethanolamine cellulose acetate as describedin U.S. Patent 2,322,085 of Yutzy; a polyacrylamide having a combinedacrylamide content of 30-60% and a specific viscosity of 025-15 on animidized polyacrylamide of like acrylamide content and viscosity asdescribed in U.S. Patent 2,541,474 of Lowe, Minsk and Kenyon; zein asdescribed in U.S. Patent 2,563,791 of Lowe; a vinyl alcohol polymercontaining urethane carboxylic acid groups of the type described in U.S.Patent 2,768,154 of Unruh and Smith, or containing cyano-acetyl groupssuch as the vinyl alcohol-vinyl cyanoacetate copolymer as described inU.S. Patent 2,808,331 of Unruh, Smith, and Priest; or a polymericmaterial which results from polymerizing a protein or a saturatedacylated protein with a monomer having a vinyl group as described inIllingsworth, Dann, and Gates U.S. Patent 2,852,382.

If desired, compatible mixtures of two or more of these colloids may beemployed for dispersing the silver halide in its preparation.

Photographic emulsions containing our couplers may be coated ontransparent supports such as glass, cellulose esters, or on anon-transparent reflecting material such as paper or opaque celluloseester.

Our yellow-colored magenta-forming 3-anilino-4-ary1- azo-5-pyrazolonecouplers described hereinabove are superior to the coloredmagenta-forming couplers known and used before to correct the undesiredblue absorption of the magenta dye formed upon color development. Theyare characterized by being completely reactive with oxidized primaryaromatic amino developing agents when they are used in emulsiondispersions having a coupler to coupler incorporating solvent ratio of1: 4 and give complete compensation for unwanted blue absorption of themagenta dye when incorporated in the proper amount. This valuablecharacteristic is very unexpected since the corresponding3-benzamido-4-arylazo-S-pyrazolone couplers which are very similarchemically to our couplers are completely unreactive at the desiredcoupler-to-coupler incorporating solvent ratio of 1:% and give no colorcorrection. Furthermore, our couplers are characterized by having anextinction coefficient of 2.8 10 in butyl acetate which is surprisinglyhigher than the extinction coeificient of 1.5 X 10 in butyl acetate forthe corresponding 3-benzamido-4-arylazo-5- pyrazolone couplers referredto above. These valuable characteristics of our couplers make itpossible to get complete color correction in emulsions containing themwith smaller amounts of coupler than is possible with couplers usedbefore. Our couplers can be coated in thinner layers which makes itpossible to produce images with lower minimum densities and thus producepictures with whiter highlights. Thinner emulsion layers are oftendesirably employed for producing images with improved definition andresolution.

This invention has been described in detail with particular reference topreferred embodiments thereof, but it will be understood that variationsand modifications can be effected within the spiirt and scope of theinvention as described hereinabove and as defined in the appendedclaims.

We claim:

1. A photographic silver halide emulsion containing a yellow-coloredmagenta-forming coupler compound selected from those having the formula:

it i" RN l I re 0 N wherein R is a member selected from the groupconsisting of a phenyl radical and halogen substituted phenyl radicals;R is a member selected from the group consisting of hydrogen atoms andalkyl radicals having l to 4 carbon atoms; X, Y, and Z are selected fromthe group consisting of hydrogen atoms and alkyl radicals having 1 to 20carbon atoms and where at least one of the substituents X, Y, and Z issaid alkyl radical; and R" is selected from the group consisting ofalkyl radicals having 1 to carbon atoms and alkoxy radicals having 1 to10 carbon atoms, and an uncolored magenta-forming pyrazolone couplerwhich forms a dye of the same hue as formed by the yellow-coloredmagenta-forming coupler upon coupling with an oxidized primary aromaticamino developing agent.

2. A photographic silver halide emulsion containing (1) a yellow-coloredmagenta-forming coupler compound selected from those having the formula:

wherein R is a member selected from the group consisting of a phenylradical and halogen substituted phenyl radicals; R is a member selectedfrom the group consisting of hydrogen atoms and alkyl radicals having 1to 4 carbon atoms; X, Y, and Z are selected from the group consisting ofhydrogen atoms and alkyl radicals having 1 to 20 carbon atoms and whereat least one of the substituents X, Y, and Z is said alkyl radical; R"is selected from the group consisting of alkyl radicals having from 1 to10 carbon atoms and alkoxy radicals having 1 to 10 carbon atoms, and (2)an uncolored magentaforming coupler which both form the same magentadye, said uncolored coupler having the formula:

gl l wherein R, R, X, Y, and Z are as defined above and where at leastone of the substituents X, Y, and Z is said alkyl radical.

3. A photographic silver halide emulsion containing a yellow-coloredmagenta-forming coupler selected from the group consisting of compoundsof the formula:

ll N wherein R is a member selected from the group consisting of phenylradicals and halogen substituted phenyl radicals; R is a member selectedfrom the group consisting of hydrogen atoms and alkyl radicals having 1to 4 carbon atoms; X, Y and Z are selected from the group consisting ofhydrogen atoms and alkyl radicals having 1 to 20 carbon atoms and whereat least one of the substituents X, Y, and Z is said alkyl radical; R"is selected from the group consisting of alkyl radicals 18 having from 1to 10 carbon atoms and alkoxy radicals having from 1 to 10 carbon atoms.

4. A photographic silver halide emulsion containing the yellow-coloredmagenta-forming coupler compound 1-(2',4',6,trichloropl1enyl) 3{4"-[a-(2"',4"-di-tertiaryamylphenoxy)-butyrarnido]anilino} 4(4"-methoxyphenyl) azo-S-pyr azolone.

5. A photographic silver halide emulsion containing theyellow-coloredmagenta-forming coupler compound1-(2',4',6',trich1orophenyl) 3{4"-[a-(2"',4"'-di-tertiaryamylphenoxy)-butyramid0]ani1ino} 4(2""-ethoxyphenyl)azo-5-pyrazolone.

6. A photographic silver halide emulsion containing the yellow-coloredmagenta-forming coupler compound 1-(2,4',6,trichlorophenyl) 3{4"-[a-(2",4"-di-tertiaryamylphenoxy)-butyramido]a11ilino} 4(4""-dodecoxyphenyl) azo-S-pyrazolone.

7. A photographic silver halide emulsion containing the yellow-coloredmagenta-forming coupler compound l-phenyl 3{4-[a-(2"',4-di-tertiaryamylphenoxy)- butyramidojanilino} 4(4"-methoxyphenyl(azo-5-py razolone.

8. A photographic silver halide emulsion containing the yellow-coloredmagenta-forming coupler compound 1-(2',4',6',trichlorophenyl) 3{4"[oc-(2"',4"'di-teltlaryarylamylphenoxy)-butyramido] anilino} 4(4""-secondaryamylphenyl) azo-S -pyrazolone.

9. A photographic silver halide emulsion containing the yellow-coloredmagentaforming coupler compound 1-(2',4',6,trichlorophenyl) 3{4-[a-(2,4"-di-tertiaryamylphenoxy)-butyramido]-ani1ino} 4(4"-methoxyphenyl) azo-S-pyrazolone and the uncolored magentaformingcoupler compound l-(2',4,6'-trichlorophenyl)-3- {4" [oc-(2"',4"'di-tertiaryamylphenoxy)butyramidolanilino}-5-pyrazolone.

10. A photographic silver halide emulsion containing the yellow-coloredmagenta-forming coupler compound l-(2,4',6,trich1orophenyl) 3{4-[ot-(2,4"'-di-tel1i aryarnylphenoxy)-butyramido] aniline} 4(2"-ethoxyphenyl)azo-5-pyrazolone, and the uncolored magentaformingcoupler compound 1-(2,4,6-trich1orophenyl)- 3-{4"[u-(2,4'-di-tertiaryamylphenoxy) butyramidoJ- anilino}-5-pyrazolone.

11. A photographic silver halide emulsion containing the yellow-coloredmagenta-forming coupler compound 1-(2,4,6',trichlorophenyl) 3{4"-[a-(2",4-di-tertiaryamylphenoxy)-butyramido]aniline} 4 (4""-dodecoxyphenyl) azo-S-pyrazolone and the uncolored magentaforming couplercompound 1-(2,4',6-trichlorophenyl)- 3{4"-[0a-(2"',4"' ditertiaryamylphenoxy)butyramido]anilino}-5-pyrazolone.

12. A photographic silver halide emulsion containing the yellow-coloredmagenta-forming coupler compound l-phenyl 3{4"-[u-(2',4'-di-tertiaryamylphenoxy)- butyramido'janilino} 4(4"-methoxyphenyl)azo-S- pyrazolone and the uncolored magenta-formingcoupler compound 1-phenyl-3-{4"-[a-(2",4"-di-tcrtiaryarylamylphenoxy)butyramido] anilino} -5 -pyrazolone.

13. A photographic silver halide emulsion containing the yellow-coloredmagenta-forming coupler compound 1-(2',4',6,trichlorophenyl) 3{4"-[a-(2,4"-di-tertiaryarylamylphenoxy)butyramido] aniline} 4(4"-secondaryamylphenyl)azo-S-pyrazolone, and the uncoloredmagenta-forming coupler compound 1-(2',4',6'-trichlor0- phenyl) 3 {4"[a-(2',4' di-tertiaryamylphenoxy)- butyramido] anilino} -5-pyrazolone.

References Cited in the file of this patent UNITED STATES PATENTS2,584,349 Heimbach Feb. 5, 1952 2,681,338 Harrison et al June 15, 19542,725,291 Graham Nov. 29, 1955 2,766,231 Bolliger Oct. 9, 1956

1. A PHOTOGRAPHIC SILVER HALIDE EMULSION CONTAINING A YELLOW-COLOREDMAGENTA-FORMING COUPLER COMPOUND SELECTED FROM THOSE HAVING THE FORMULA: